WO1996037522A1 - Polymers of olefinically unsaturated monomers - Google Patents
Polymers of olefinically unsaturated monomers Download PDFInfo
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- WO1996037522A1 WO1996037522A1 PCT/EP1996/001964 EP9601964W WO9637522A1 WO 1996037522 A1 WO1996037522 A1 WO 1996037522A1 EP 9601964 W EP9601964 W EP 9601964W WO 9637522 A1 WO9637522 A1 WO 9637522A1
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- polymers
- radicals
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- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 title claims abstract description 22
- 230000000737 periodic effect Effects 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 compounds olefins Chemical group 0.000 claims description 33
- 125000004429 atom Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 150000001336 alkenes Chemical group 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 150000001993 dienes Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- WBMJFMFJCWPAIT-UHFFFAOYSA-N ditert-butyl(ditert-butylphosphanylmethyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CP(C(C)(C)C)C(C)(C)C WBMJFMFJCWPAIT-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 150000005840 aryl radicals Chemical class 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 206010029719 Nonspecific reaction Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000005350 bicyclononyls Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- OWFLJHJHQKHZJR-UHFFFAOYSA-N dicyclohexyl(dicyclohexylphosphanylmethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CP(C1CCCCC1)C1CCCCC1 OWFLJHJHQKHZJR-UHFFFAOYSA-N 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical group O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical class P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Definitions
- the present invention relates to polymers obtainable by polymerizing olefinically unsaturated monomers in the presence of a metal complex of the general formula (I)
- M is a metal from group VIIIB of the Periodic Table of the Elements
- E 1 , E 2 an element from group VA of the periodic table of the elements
- a bridging structural unit consisting of one, two or three substructural units of elements from group IVA, VA, VIA of the periodic table of the elements,
- R 1 to. R 4 substituents selected from the group consisting of Ci- to C o -carbon organic and C 3 - to C 3 o -silicon organic radicals, the radicals being one or more elements from groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements can contain
- the invention also relates to a process for the preparation of these polymers; Films, fibers and moldings made from these polymers, and the use of the polymers according to the invention as films, fibers and moldings.
- polymerization of olefinically unsaturated monomers for example ethylene, C 3 - to C ⁇ -alk-1-enes and acrylic acid derivatives
- olefinically unsaturated monomers for example ethylene, C 3 - to C ⁇ -alk-1-enes and acrylic acid derivatives
- the polymerization of the olefins is catalyzed, inter alia, by mixed catalysts composed of compounds of the early transition metals (titanium, zirconium, etc.) and alkyl compounds of the main group metals (eg aluminum alkyls) - so-called Ziegler catalysts - or else by free-radical initiators , or initiated.
- mixed catalysts composed of compounds of the early transition metals (titanium, zirconium, etc.) and alkyl compounds of the main group metals (eg aluminum alkyls) - so-called Ziegler catalysts - or else by free-radical initiators , or initiated.
- Ziegler catalysts have some disadvantages. They generally react, sometimes very violently, with moisture and oxygen, their catalytic activity generally being lost.
- these catalysts are generally unable to (co) polymerize unsaturated compounds which contain functional groups such as, for example, carboxylic acid groups or ester groups.
- the polymerization of cyclic, olefinically unsaturated monomers or else of polyolefinically unsaturated, linear monomers often does not take place in the desired sense, namely as a polyinsertion reaction, but side reactions occur, such as ring opening of the cyclic monomer or ring formation of the linear monomer.
- the resulting polymers have a high inconsistency in both the chemical composition and the molecular weight distribution.
- Radical initiators are generally under high pressure, for example able to copolymerize olefins with polar, unsaturated monomers, but the incorporation of the comonomer is often inconsistent and the polymer structure is branched, which leads, for example, to a lower polymer film quality. These characteristics limit the range of application of the resulting polymers which are obtained by the various polymerization processes, and it is therefore desirable to look for alternative polymers which do not have the stated disadvantages or only to a minor extent ⁇ sen.
- EP-A 0 589 527 describes catalyst systems for olefin homopolymerization and olefin copolymerization based on special palladium-phosphine complexes.
- polar solvents such as methanol, ethylene glycol or water
- non-polar solvents such as diethylene glycol dimethyl ether (diglyme)
- maximum molar masses Mn of 5600 are achieved, but only traces of the comonomer are then incorporated.
- the use of internal olefins has also not been described, and the double bond content of the polymers and their molar mass distribution Mw / Mn are also not disclosed.
- EP-A 0 454 231 describes catalyst systems for the polymerization of ethylene, olefins and alkynes based on cationic metal complexes of late transition metals (Group VIII).
- Group VIII late transition metals
- the object of the present invention was to provide new polymers which do not have the disadvantages described and which contain polar comonomers which are built in in a predominantly linear sequence.
- polymers which can be obtained by polymerizing olefinically unsaturated monomers in the presence of a metal complex of the general formula (I) in which the substituents and indices have the following meaning:
- M is a metal from group VIIIB of the Periodic Table of the Elements
- E i , E 2 an element from group VA of the periodic table of the elements
- a bridging structural unit consisting of one, two or three substructural units from elements of group IVA, VA, VIA of the periodic table of the elements,
- R l to R 4 substituents selected from the group consisting of C ⁇ ⁇ to C 2 o ⁇ organic carbon and C 3 - to C 3 o-organosilicon radicals, the radicals being one or more elements from group IVA, VA, VIA and VIIA of the periodic table of the elements,
- Suitable metals M of the metal complexes according to the invention are the metals from group VIIIB of the periodic table of the elements, ie, in addition to iron, cobalt and nickel, primarily the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum and very particularly palladium.
- the metals can be present in the complexes formally uncharged, formally single positively charged, or formally double positively charged.
- the elements E 1 and E 2 are the elements of the 5th main group of the Periodic Table of the Elements (group VA), i.e. nitrogen,
- the chelate compound can contain different elements E 1 and E 2 , for example nitrogen and phosphorus.
- the bridging structural unit Z is an atomic grouping that connects the two elements E 1 and E 2 to one another.
- An atom or two or three atoms from group IVA, VA or VA of the Periodic Table of the Elements form the connecting bridge between E 1 and E 2 .
- Possible free valences of these bridge atoms can be saturated in a variety of ways, for example by substitution with hydrogen, elements from group IVA, VA, VIA or VIIA of the periodic table of the elements. These substituents can also form a ring with one another or with the bridge atom.
- group IVA of the Periodic Table of the Elements such as methylene (-CH 2 -), 1,2-ethylene (-CH 2 -CH 2 -), 1 , 3-propylene (-CH 2 -CH 2 -CH 2 -), 1,3-disilopropylene (-R 2 Si
- Particularly suitable bridging structural units are those with only one bridging atom, such as —CR 5 R 6 - or —SiR 5 R 6 - in which R 5 and R 6 are hydrogen and Cj . - until C ⁇ 0 -carbon organic residue.
- R 5 and R 6 can also form a 3- to 10-membered ring together with the bridge atom.
- Suitable carbon-organic radicals R x to R 4 are aliphatic, cycloaliphatic and aromatic with 1 to 20 C atoms, for example the methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl and 1-octyl group.
- Linear arylalkyl groups each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical are also suitable, such as, for example, benzyl and aryl radicals, such as, for example, phenyl, tolyl and other substituted phenyl groups.
- the radicals R i to R 4 should preferably be sufficiently space-filling that the central atom, for example the palladium atom, with which the atoms Egg and E 2 form the active complex, is largely shielded. Residues that meet this requirement are, for example, cycloaliphatic radicals and branched aliphatic radicals, including in particular those with branching in the ⁇ position.
- the cycloaliphatic radicals are the cyclopentyl, cyclohexyl and menthyl groups, and especially bicyclic radicals such as the norbornyl, pinanyl, bornyl and bicyclononyl groups in any combination of the ring structure with the atoms E 1 and E 2 .
- the cycloaliphatic radicals preferably contain a total of 5 to 20 carbon atoms.
- branched aliphatic radicals are C 3 - to C 2 o ⁇ , preferably C 3 - to -C 2 alkyl, such as the iso-propyl, iso-butyl, sec-butyl, neopentyl and tert-butyl group, furthermore alkylaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.
- the tert-butyl group, the iso-propyl group, the sec-butyl group and the menthyl group are particularly suitable.
- Alkyl groups with branching further out are also very suitable as substituents R 1 to R 4 , such as the isobutyl, 3-methyl-but-2-yl and 4-methylpentyl group.
- radicals R x to R 4 are not of decisive importance according to the previous observations, ie the radicals can also contain atoms from the group IVA, VA, VIA or VIIA of the periodic system of the elements, such as for example halogen, oxygen, sulfur, nitrogen, silicon, here for example the bis (trimethylsilyl) methyl group.
- Functional groups such as, for example, hydroxy, alkoxy and cyano, which are inert under the polymerization conditions, can also be considered in this context.
- Preferred hetero substituents R 1 to R 4 are C 3 - to C 3 o-organosilicon radicals, that is to say tetravalent silicon atoms which are bonded to E 1 or E 2 and whose remaining valences are saturated with three carbon-organic radicals, the sum of the carbon atoms of these three silicon bonded residues are in the range of three to thirty.
- Examples include the trimethylsilyl, tert-butyldimethylsilyl or triphenylsilyl group, in particular the trimethylsilyl group.
- Diphosphanes which are bridged with a methylene group are preferably used as the chelating ligand; particularly preferably with C 3 - to Cio-cycloaliphatic or branched C 3 - to C rj-aliphatic radicals R 1 to R 4 substituted methylene-bridged diphosphines, such as for example bis (di-tert-butylphosphino) methane, [(Di tert-butylphosphino) (di-cyclohexylphosphino] methane or bis (di-cyclohexylphosphino) methane, the suitability of which for the process according to the invention is currently attributed to the methylene linkage of the two phosphorus atoms and the spatial structure of the radicals R 1 to R 4 .
- a very particularly preferred compound as the chelating ligand is bis (di-tert-butylphosphino) methane.
- the ligands L 1 , L 2 carry one or two formally negative charges, or if the metal is formally uncharged, the ligands L i , L 2 are also formally uncharged.
- the chemical nature of the ligands is not critical. According to the current state of knowledge, they have the function of stabilizing the rest of the metal complex against decomposition, for example deposition of the metal or non-specific reactions, for example aggregation of the complex fragments.
- Suitable formally charged inorganic ligands L 1 , L 2 are halides, sulfates, phosphates or nitrates.
- Halides such as chlorides, bromides, iodides and in particular chlorides are preferably used.
- Suitable formally charged organic ligands L 1 , L 2 are C 1 to C 0 aliphatic, C 3 to C 30 cycloaliphatic, C to C 20 aralkyl radicals with C 6 to C 0 aryl radical and C 1 to C 10 -Alkylrest, C- 6 - to C o ⁇ aromatic residues, such as methyl, ethyl propyl, isopropyl, tert-butyl, neo-pentyl, cyclohexyl, benzyl, neophyl, phenyl and substituted phenyl residues.
- organic ligands L 1 , L 2 -C ⁇ ⁇ C o ⁇ carboxylates such as acetate, propionate, oxalate, benzoate, citrate and salts of organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate.
- organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate.
- Lewis bases that is to say compounds with a free pair of electrons, are generally suitable as formally uncharged ligands L 1 , L 2 .
- Lewis bases whose free electron pair or whose free electron pairs are located on a nitrogen or oxygen atom ie, for example, nitriles, R-CN, ketones, ethers, alcohols, are particularly suitable.
- acetonitrile or tetrahydrofuran is used.
- the metal complex (I) contains anions. If the M-containing complex fragment is formally uncharged, the complex according to the invention contains no anion X.
- Suitable anions X are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as, for example, methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate , furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyDborat, hexafluorophosphate, hexafluoroarsenate
- perchlorate trifluoroacetate, sulfonates such as methylsulfonate, trifluoromethyl or toluene fluoronafluorophenate, pentafluorofluorate, pentafluorophenate, pentafluorophorate, Toluenesulfonate.
- ethylene and C 3 -C 1 -alk-1-enes such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen and 1-decene.
- Internal E or Z olefins such as 2-butene, 2-pentene, 2- and 3-hexene can also be used advantageously; dienes such as 1,3-butadiene, 1,4-hexadiene, 1, 5-hexadiene, and also cycloolefins such as cyclopentene, cyclohexene, norbornene and norbornadiene, cyclopentadiene and dicyclopentadiene.
- styrene and .alpha.-methylstyrene may be mentioned primarily.
- Olefins substituted with functional groups are also particularly important as monomers.
- Possible functional groups are the carboxyl group, -COOH and their derivatives, such as esters, halides and amides, furthermore the hydroxyl group, the cyano group, -CN, keto group, aldehyde group and carboxylate group as well as the silyl group, -SiR 3 , where R is hydrogen or an organic radical having 1 to 15 carbon atoms.
- Particularly suitable olefins substituted with functional groups are acrylic acid and methacrylic acid and their derivatives, including in particular the nitriles, the amides and the C 1 -C 8 -alkyl esters such as, for example, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tert. -Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate.
- Other suitable monomers are vinyl chloride, vinyl acetate, vinyl propionate, maleic anhydride and N-vinyl pyrrolidone.
- the molar ratio between the different monomers can largely be chosen freely.
- the polymerization conditions are not critical per se.
- the polymerizations can be carried out batchwise or continuously.
- Catalyst systems can be carried out in the gas phase, in suspension, in liquid and in supercritical monomers and in solvents which are inert under the polymerization conditions.
- Suitable inert solvents are alcohols such as methanol, ethanol, propanol, i-propanol, 1-butanol and tert-butanol, sulfoxides and sulfones, for example dimethyl sulfoxide, esters such as Ethyl acetate and butyrolactone, ethers such as tetrahydrofuran, dimethylethylene glycol and diisopropyl ether and aromatic solvents such as benzene, toluene, ethylbenzene or chlorobenzene or mixtures thereof.
- alcohols such as methanol, ethanol, propanol, i-propanol, 1-butanol and tert-butanol
- sulfoxides and sulfones for example dimethyl sulfoxide
- esters such as Ethyl acetate and butyrolactone
- ethers such as tetrahydrofuran
- the molecular weight of the polymers according to the invention can be regulated in a customary manner by varying the polymerization temperature and by adding hydrogen.
- the polymers produced using the process according to the invention are generally distinguished by a high molar mass, narrow molar mass distribution and high proportion of double bonds.
- the polymers are suitable for the production of moldings, in particular moldings for packaging and for films and fibers and for adhesion promoters, and can be easily chemically modified on account of their reactive double bonds.
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
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Abstract
Polymers are obtained by polymerising olefinically unsaturated monomers in the presence of a metal complex having the general formula (I), in which the substituents and indexes have the following meanings: M is a metal of group VIIIB of the periodic table of elements; E1, E2 stand for an element of group VA of the periodic table of elements; Z is a bridging structural unit made of one, two or three substructural units of elements of groups IVA, VA, VIA of the periodic table of elements; R1 to R4 stand for substituents selected in the group that consists of C¿1?-C20 organic carbon residues and C3-C30 organic silicium residues which may contain one or several elements of groups IVA, VA, VIA and VIIA of the periodic table of elements; L?1, L2¿ stand for formally charged or neutral ligands; X stands for monovalent or polyvalent anions; p equals 0, 1 or 2; m, n equal 0, 1 or 2, whereas p = m x n.
Description
Polymere aus olefinisch ungesättigten MonomerenPolymers from olefinically unsaturated monomers
Beschreibungdescription
Die vorliegende Erfindung betrifft Polymere, erhältlich durch Po¬ lymerisation von olefinisch ungesättigten Monomeren in Gegenwart eines Metallkomplexes der allgemeinen Formel (I)The present invention relates to polymers obtainable by polymerizing olefinically unsaturated monomers in the presence of a metal complex of the general formula (I)
M ein Metall aus der Gruppe VIIIB des Perioden¬ systems der ElementeM is a metal from group VIIIB of the Periodic Table of the Elements
E1, E2 ein Element aus der Gruppe VA des Periodensystems der Elemente,E 1 , E 2 an element from group VA of the periodic table of the elements,
eine verbrückende Struktureinheit aus einer, zwei oder drei Substruktureinheiten von Elementen der Gruppe IVA, VA, VIA des Periodensystems der Ele¬ mente,a bridging structural unit consisting of one, two or three substructural units of elements from group IVA, VA, VIA of the periodic table of the elements,
R1 bis. R4 Substituenten, ausgewählt aus der Gruppe bestehend aus Ci- bis C o-Kohlenstofforganischen und C3- bis C3o-Siliciumorganischen Resten, wobei die Reste ein Element oder mehrere Elemente der Gruppe IVA, VA, VIA und VIIA des Periodensystems der Elemente ent¬ halten können,R 1 to. R 4 substituents selected from the group consisting of Ci- to C o -carbon organic and C 3 - to C 3 o -silicon organic radicals, the radicals being one or more elements from groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements can contain
Ll, 2 formal geladene oder neutrale LigandenL l , 2 formally charged or neutral ligands
ein- oder mehrwertige Anionenmono- or polyvalent anions
0, 1 oder 20, 1 or 2
m, n 0, 1 oder 2
wobei p = m x nm, n 0, 1 or 2 where p = mxn
Außerdem betrifft die Erfindung ein Verfahren zur Herstellung dieser Polymeren; Folien, Fasern und Formkörper aus diesen Poly- meren, sowie die Verwendung der erfindungsgemäßen Polymeren als Folien, Fasern und Formkörper.The invention also relates to a process for the preparation of these polymers; Films, fibers and moldings made from these polymers, and the use of the polymers according to the invention as films, fibers and moldings.
Die Polymerisation von olefinisch ungesättigten Monomeren, bei¬ spielsweise von Ethylen, C3- bis Cβ-Alk-1-enen und Acrylsäure- derivaten ist für unterschiedliche Polymerisationsverfahren gut bekannt, und die erhältlichen Polyolefine werden weithin in vie¬ len Anwendungsgebieten, zum Beispiel als Folien, Formkörper und Fasern kommerziell verwendet.The polymerization of olefinically unsaturated monomers, for example ethylene, C 3 - to Cβ-alk-1-enes and acrylic acid derivatives, is well known for different polymerization processes, and the polyolefins obtainable are widely used in many fields of application, for example as Films, moldings and fibers used commercially.
Die Polymerisation der Olefine wird, unter anderem, durch Misch¬ katalysatoren aus Verbindungen der frühen Übergangsmetalle (Ti¬ tan, Zirconium etc.) und Alkylverbindungen der Hauptgruppen¬ metalle (z.B. Aluminiumalkyle) - sogenannte Ziegler-Katalysatoren - oder aber auch durch radikalische Initiatoren katalysiert, bzw. initiiert.The polymerization of the olefins is catalyzed, inter alia, by mixed catalysts composed of compounds of the early transition metals (titanium, zirconium, etc.) and alkyl compounds of the main group metals (eg aluminum alkyls) - so-called Ziegler catalysts - or else by free-radical initiators , or initiated.
Ziegler-Katalysatoren haben jedoch einige Nachteile. Sie reagie¬ ren in der Regel, teilweise sehr heftig, mit Feuchtigkeit und Sauerstoff, wobei ihre katalytische Aktivität im allgemeinen ver- loren geht.However, Ziegler catalysts have some disadvantages. They generally react, sometimes very violently, with moisture and oxygen, their catalytic activity generally being lost.
Weiterhin sind diese Katalysatoren im allgemeinen nicht in der Lage, ungesättigte Verbindungen, welche funktioneile Gruppen, wie zum Beispiel Carbonsäuregruppen oder Estergruppen enthalten, zu (co)polymerisieren.Furthermore, these catalysts are generally unable to (co) polymerize unsaturated compounds which contain functional groups such as, for example, carboxylic acid groups or ester groups.
Auch läuft die Polymerisation von cyclischen, olefinisch ungesättigten Monomeren oder aber von mehrfach olefinisch ungesättigten, linearen Monomeren oft nicht im gewünschten Sinne, nämlich als Polyinsertionsreaktion ab, sondern es treten Neben¬ reaktionen auf, wie Ringöffnung des cyclischen Monomeren oder Ringbildung des linearen Monomeren. Die dabei entstandenen Poly¬ mere weisen eine hohe Uneinheitlichkeit sowohl der chemischen Zusammensetzung als auch der Molekulargewichtsverteilung auf.The polymerization of cyclic, olefinically unsaturated monomers or else of polyolefinically unsaturated, linear monomers often does not take place in the desired sense, namely as a polyinsertion reaction, but side reactions occur, such as ring opening of the cyclic monomer or ring formation of the linear monomer. The resulting polymers have a high inconsistency in both the chemical composition and the molecular weight distribution.
Radikalische Initiatoren sind im allgemeinen unter hohem Druck, in der Lage beispielsweise Olefine mit polaren, ungesättigten Mo¬ nomeren zu copolymerisieren, jedoch ist der Einbau des Comono- meren oft uneinheitlich und die Polymerstruktur verzweigt, welches beispielsweise zu einer geringeren Polymerfolienqualität führt.
Durch diese Charakteristika ist der Anwendungsbereich der resul¬ tierenden Polymeren, die nach den verschiedenen Polymerisations- verfahren erhalten werden eingeschränkt, und es ist daher wün¬ schenswert nach alternativen Polymeren zu suchen, welche die ge- nannten N chteile nicht oder nur in untergeordnetem Maße aufwei¬ sen.Radical initiators are generally under high pressure, for example able to copolymerize olefins with polar, unsaturated monomers, but the incorporation of the comonomer is often inconsistent and the polymer structure is branched, which leads, for example, to a lower polymer film quality. These characteristics limit the range of application of the resulting polymers which are obtained by the various polymerization processes, and it is therefore desirable to look for alternative polymers which do not have the stated disadvantages or only to a minor extent ¬ sen.
EP-A 0 589 527 beschreibt Katalysatorsysteme für die Olefin-Homo- Polymerisation und Olefin-Copolymerisation auf der Basis- von spe- ziellen Palladium-Phosphankomplexen. Sowohl die präparative Zugänglichkeit als auch das Polymerisationsverhalten dieser Katalysatoren lassen jedoch zu wünschen übrig. So erhält man in polaren Lösungsmitteln wie Methanol, Ethylenglykol oder Wasser nur geringe Polymerisationsgrade (Oligomere mit 3 bis 20 Monomer- einheiten) . Aber auch in unpolaren Solventien wie Diethylengly- coldimethylether (Diglyme) werden nur maximale Molmassen Mn von 5600 erreicht, wobei dann aber nur Spuren des Comonomeren einge¬ baut werden. Die Verwendung von internen Olefinen ist darüber hinaus nicht beschrieben, und der Doppelbindungsgehalt der Poly- meren und deren Molmassenverteilung Mw/Mn ist ebenfalls nicht offenbart.EP-A 0 589 527 describes catalyst systems for olefin homopolymerization and olefin copolymerization based on special palladium-phosphine complexes. However, both the preparative accessibility and the polymerization behavior of these catalysts leave something to be desired. In polar solvents such as methanol, ethylene glycol or water, only low degrees of polymerization are obtained (oligomers with 3 to 20 monomer units). However, even in non-polar solvents such as diethylene glycol dimethyl ether (diglyme), only maximum molar masses Mn of 5600 are achieved, but only traces of the comonomer are then incorporated. The use of internal olefins has also not been described, and the double bond content of the polymers and their molar mass distribution Mw / Mn are also not disclosed.
EP-A 0 454 231 beschreibt Katalysatorsysteme für die Polymerisa¬ tion von Ethylen, Olefinen und Alkinen auf der Basis von kat- ionischen Metallkomplexen von späten Übergangsmetallen (Gruppe VIII) . Diese Katalysatoren sind aber Verunreinigungen gegenüber sehr empfindlich. Die erreichbaren Produktivitäten lassen eben¬ falls zu wünschen übrig. Es werden keine polaren Copolymerisate beschrieben.EP-A 0 454 231 describes catalyst systems for the polymerization of ethylene, olefins and alkynes based on cationic metal complexes of late transition metals (Group VIII). However, these catalysts are very sensitive to contamination. The achievable productivity also leaves something to be desired. No polar copolymers are described.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, neue Poly¬ mere zur Verfügung zu stellen, die die geschilderten Nachteile nicht aufweisen und die insbesondere in überwiegend linearer Se¬ quenz eingebaute polare Comonomere enthalten.The object of the present invention was to provide new polymers which do not have the disadvantages described and which contain polar comonomers which are built in in a predominantly linear sequence.
Demgemäß wurden Polymere, erhältlich durch Polymerisation von olefinisch ungesättigten Monomeren in Gegenwart eines Metallkom¬ plexes der allgemeinen Formel (I)
in der die Substituenten und Indizes folgende Bedeutung haben :Accordingly, polymers which can be obtained by polymerizing olefinically unsaturated monomers in the presence of a metal complex of the general formula (I) in which the substituents and indices have the following meaning:
M ein Metall aus der Gruppe VIIIB des Perioden¬ systems der ElementeM is a metal from group VIIIB of the Periodic Table of the Elements
Ei, E2 ein Element aus der Gruppe VA des Periodensystems der Elemente,E i , E 2 an element from group VA of the periodic table of the elements,
eine verbrückende Struktureinheit aus einer, zwei oder drei Substruktureinheiten von Elementen der Gruppe IVA, VA, VIA des Periodensystems der Elemente,a bridging structural unit consisting of one, two or three substructural units from elements of group IVA, VA, VIA of the periodic table of the elements,
Rl bis R4 Substituenten, ausgewählt aus der Gruppe bestehend aus Cχ~ bis C2o~kohlenstofforganischen und C3- bis C3o-siliciumorganischen Reste, wobei die Reste ein Element oder mehrere Elemente der Gruppe IVA, VA, VIA und VIIA des Periodensystems der Elemente ent¬ halten können,R l to R 4 substituents selected from the group consisting of Cχ ~ to C 2 o ~ organic carbon and C 3 - to C 3 o-organosilicon radicals, the radicals being one or more elements from group IVA, VA, VIA and VIIA of the periodic table of the elements,
, L2 formal geladene oder neutrale Liganden, L 2 formally charged or neutral ligands
ein- oder mehrwertige Anionenmono- or polyvalent anions
P 0, 1 oder 2P 0, 1 or 2
m, n 0, 1 oder 2m, n 0, 1 or 2
wobei p = m x nwhere p = m x n
gefunden.found.
Außerdem wurde das eingangs definierte Verfahren zur Herstellung der Polymeren, deren Verwendung zur Herstellung von Folien, Fa- sern und Formkörpern, sowie die Folien, Fasern und Formkörper ge¬ funden.
Als Metalle M der erfindungsgemäßen Metallkomplexe eignen sich die Metalle der Gruppe VIIIB des Periodensystems der Elemente, also neben Eisen, Cobalt und Nickel vornehmlich die Platinmetalle wie Ruthenium, Rhodium, Osmium, Iridium und Platin sowie ganz be- sonders Palladium. Die Metalle können in den Komplexen formal un¬ geladen, formal einfach positiv geladen, oder formal zweifach po¬ sitiv geladen vorliegen.In addition, the process defined at the outset for the production of the polymers, their use for the production of films, fibers and moldings, and also the films, fibers and moldings, was found. Suitable metals M of the metal complexes according to the invention are the metals from group VIIIB of the periodic table of the elements, ie, in addition to iron, cobalt and nickel, primarily the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum and very particularly palladium. The metals can be present in the complexes formally uncharged, formally single positively charged, or formally double positively charged.
Als Elemente E1 und E2 kommen die Elemente der V. Hauptgruppe des Periodensystems der Elemente (Gruppe VA), also Stickstoff,The elements E 1 and E 2 are the elements of the 5th main group of the Periodic Table of the Elements (group VA), i.e. nitrogen,
Phosphor, Arsen, Antimon, oder Bismut in Betracht. Besonders ge¬ eignet sind Stickstoff oder Phosphor, insbesondere Phosphor. Die Chelatverbindung kann unterschiedliche Elemente El und E2 enthal¬ ten, so zum Beispiel Stickstoff und Phosphor.Phosphorus, arsenic, antimony, or bismuth. Nitrogen or phosphorus, in particular phosphorus, are particularly suitable. The chelate compound can contain different elements E 1 and E 2 , for example nitrogen and phosphorus.
Die verbrückende Struktureinheit Z ist eine Atomgruppierung, die die beiden Elemente E1 und E2 miteinander verbindet. Ein Atom oder zwei oder drei Atome aus der Gruppe IVA, VA oder VA des Perioden¬ systems der Elemente bilden die verbindende Brücke zwischen E1 und E2. Mögliche freie Valenzen dieser Brückenatome können mannig¬ faltig abgesättigt sein, so zum Beispiel durch Substitution mit Wasserstoff, Elementen aus der Gruppe IVA, VA, VIA oder VIIA des Periodensystems der Elemente. Diese Substituenten können auch un¬ tereinander oder mit dem Brückenatom einen Ring bilden.The bridging structural unit Z is an atomic grouping that connects the two elements E 1 and E 2 to one another. An atom or two or three atoms from group IVA, VA or VA of the Periodic Table of the Elements form the connecting bridge between E 1 and E 2 . Possible free valences of these bridge atoms can be saturated in a variety of ways, for example by substitution with hydrogen, elements from group IVA, VA, VIA or VIIA of the periodic table of the elements. These substituents can also form a ring with one another or with the bridge atom.
Gut geeignete verbrückende Struktureinheiten sind solche mit einem, zwei oder drei Elementen aus der Gruppe IVA des Perioden¬ systems der Elemente wie zum Beispiel Methylen (-CH2-) , 1,2- Ethylen (-CH2-CH2-), 1,3-Propylen (-CH2-CH2-CH2-) , 1,3-Disila- propylen (-R2Si-CH2-SiR2-) , mit R=Wasserstoff, Ci-bis Cio-kohlen- stofforganischer Rest), Ethyliden (CH3(H)C=), 2-Propyliden ((CH3) C=)> Diphenylmethylen ((C6Hs)2C=) oder ortho-Phenylen.Suitable bridging structural units are those with one, two or three elements from group IVA of the Periodic Table of the Elements, such as methylene (-CH 2 -), 1,2-ethylene (-CH 2 -CH 2 -), 1 , 3-propylene (-CH 2 -CH 2 -CH 2 -), 1,3-disilopropylene (-R 2 Si-CH 2 -SiR 2 -), with R = hydrogen, Ci- to Cio-carbon- organic residue), ethylidene (CH 3 (H) C =), 2-propylidene ((CH 3 ) C =) > diphenylmethylene ((C 6 Hs) 2 C =) or ortho-phenylene.
Als besonders geeignete verbrückende Struktureinheiten seien solche mit nur einem verbrückenden Atom genannt wie -CR5R6- oder -SiR5R6- worin R5 und R6 für Wasserstoff und Cj.- bis Cι0-kohlen- stofforganischer Rest steht. R5 und R6 können auch zusammen mit dem Brückenatom einen 3- bis 10-gliedrigen Ring bilden. Beispiel¬ haft seien als einatomig verbrückende Struktureinheiten genannt Methylen (-CH2-) , Ethyliden (CH3(H)C=), 2-Propyliden ((CH3)2C=), Diphenylmethylen ((C6H5)2C=), Dialkylsilylen, wie Dimethylsilylen, Diphenylsilylen; weiterhin als cyclysche Brückenglieder Cyclopro- pyliden, Cyclobutyliden, Cyclopentyliden, Cyclohexyliden. Bevorzugte verbrückende Struktureinheiten sind Methylen (-CH2-) , Ethyliden (CH3(H)C=), 2-Propyliden ((CH3)2C=), Dimethylsilylen, Diphenylsilylen, insbesondere Methylen.
Als kohlenstofforganische Reste Rx bis R4 kommen aliphatische sowie cycloaliphatische und aromatische mit 1 bis 20 C-Atomen in Betracht, beispielsweise die Methyl-, Ethyl-, 1-Propyl-, 1-Butyl-, 1-Pentyl, 1-Hexyl- und 1-Octylgruppe. Ferner sind li- neare Arylalkylgruppen mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest geeignet, wie beispielsweise Benzyl- sowie Arylreste wie zum Beispiel Phenyl, Tolyl und andere substituierte Phenylgruppen. Die Reste Ri bis R4 sollen vorzugsweise soweit raumerfüllend sein, daß das Zentralatom, z.B. das Palladiumatom, mit dem die Atome Ei und E2 den aktiven Komplex bilden, weithin abgeschirmt wird. Re¬ ste, welche dieser Forderung genügen, sind beispielsweise cyclo¬ aliphatische Reste sowie verzweigte aliphatische Reste, darunter besonders solche mit Verzweigung in α-Position.Particularly suitable bridging structural units are those with only one bridging atom, such as —CR 5 R 6 - or —SiR 5 R 6 - in which R 5 and R 6 are hydrogen and Cj . - until Cι 0 -carbon organic residue. R 5 and R 6 can also form a 3- to 10-membered ring together with the bridge atom. Examples of structural units bridging one atom are methylene (-CH 2 -), ethylidene (CH 3 (H) C =), 2-propylidene ((CH 3 ) 2 C =), diphenylmethylene ((C 6 H 5 ) 2 C =), dialkylsilylene, such as dimethylsilylene, diphenylsilylene; also as cyclic bridge members cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene. Preferred bridging structural units are methylene (-CH 2 -), ethylidene (CH 3 (H) C =), 2-propylidene ((CH 3 ) 2 C =), dimethylsilylene, diphenylsilylene, especially methylene. Suitable carbon-organic radicals R x to R 4 are aliphatic, cycloaliphatic and aromatic with 1 to 20 C atoms, for example the methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl and 1-octyl group. Linear arylalkyl groups each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical are also suitable, such as, for example, benzyl and aryl radicals, such as, for example, phenyl, tolyl and other substituted phenyl groups. The radicals R i to R 4 should preferably be sufficiently space-filling that the central atom, for example the palladium atom, with which the atoms Egg and E 2 form the active complex, is largely shielded. Residues that meet this requirement are, for example, cycloaliphatic radicals and branched aliphatic radicals, including in particular those with branching in the α position.
Als cycloaliphatische Reste kommen die Cyclopentyl-, Cyclohexyl- gruppen und Menthylgruppen sowie besonders bicyclische Reste wie die Norbornyl-, Pinanyl-, Bornylgruppe und Bicyclononylgruppe in beliebiger Verknüpfung des Ringgerüstes mit den Atomen El und E2 in Betracht. Vorzugsweise enthalten die cycloaliphatischen Reste insgesamt 5 bis 20 C-Atome.The cycloaliphatic radicals are the cyclopentyl, cyclohexyl and menthyl groups, and especially bicyclic radicals such as the norbornyl, pinanyl, bornyl and bicyclononyl groups in any combination of the ring structure with the atoms E 1 and E 2 . The cycloaliphatic radicals preferably contain a total of 5 to 20 carbon atoms.
Als verzweigte aliphatische Reste eignen sich C3- bis C2o~, vor¬ zugsweise C3- bis Cι2-Alkylreste, wie zum Beispiel die iso-Pro- pyl-, iso-Butyl-, sec.-Butyl-, Neopentyl-und tert.-Butylgruppe, weiterhin Alkylaryl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest.As branched aliphatic radicals are C 3 - to C 2 o ~, preferably C 3 - to -C 2 alkyl, such as the iso-propyl, iso-butyl, sec-butyl, neopentyl and tert-butyl group, furthermore alkylaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.
Besonders geeignet sind die tert.-Butylgruppe, die iso-Propyl- gruppe, die sec.-Butylgruppe und die Menthylgruppe.The tert-butyl group, the iso-propyl group, the sec-butyl group and the menthyl group are particularly suitable.
Auch Alkylgruppen mit weiter außen liegender Verzweigung sind als Substituenten Ri bis R4 gut geeignet, wie die iso-Butyl-, die 3-Methyl-but-2-yl- und 4-Methylpentylgruppe.Alkyl groups with branching further out are also very suitable as substituents R 1 to R 4 , such as the isobutyl, 3-methyl-but-2-yl and 4-methylpentyl group.
Auf die chemische Natur der Reste Rx bis R4 kommt es nach den bis¬ herigen Beobachtungen nicht entscheidend an, d.h. die Reste kön¬ nen auch Atome aus der Gruppe IVA, VA, VIA oder VIIA des Perio¬ densystems der Elemente enthalten, wie zum Beispiel Halogen, Sauerstoff, Schwefel, Stickstoff, Silicium, hier beispielsweise die Bis (trimethylsilyl)methylgruppe. Auch funktionelle Gruppen wie zum Beispiel Hydroxy, Alkoxy und Cyan, die sich unter den Po¬ lymerisationsbedingungen inert verhalten, kommen in diesem Zu¬ sammenhang in Betracht.
Bevorzugte Heterosubstituenten R1 bis R4 sind C3- bis C3o-Siliciumorganische Reste, das heißt tetravalente Siliciumatome die an E1 oder E2 gebunden sind und deren übrige Valenzen mit drei Kohlenstofforganischen Resten abgesättigt sind, wobei die Summe der Kohlenstoffatome dieser drei an Silicium gebundenen Reste im Bereich von drei bis dreißig liegt. Beispielsweise seien genannt die Trimethylsilyl-, tert.-Butyldimethylsilyl- oder Triphenyl- silylgruppe, insbesondere die Trimethylsilylgruppe.The chemical nature of the radicals R x to R 4 is not of decisive importance according to the previous observations, ie the radicals can also contain atoms from the group IVA, VA, VIA or VIIA of the periodic system of the elements, such as for example halogen, oxygen, sulfur, nitrogen, silicon, here for example the bis (trimethylsilyl) methyl group. Functional groups such as, for example, hydroxy, alkoxy and cyano, which are inert under the polymerization conditions, can also be considered in this context. Preferred hetero substituents R 1 to R 4 are C 3 - to C 3 o-organosilicon radicals, that is to say tetravalent silicon atoms which are bonded to E 1 or E 2 and whose remaining valences are saturated with three carbon-organic radicals, the sum of the carbon atoms of these three silicon bonded residues are in the range of three to thirty. Examples include the trimethylsilyl, tert-butyldimethylsilyl or triphenylsilyl group, in particular the trimethylsilyl group.
Vorzugsweise verwendet man als Chelatligand Diphosphane welche mit einer Methylengruppe verbrückt sind; besonders bevorzugt mit C3- bis Cio-cycloaliphatischen oder verzweigten C3- bis C rj-alipha- tischen Resten R1 bis R4 substituierte methylenverbrückte Diphos¬ phane, wie beispielsweise Bis (di-tert.-butylphosphino)methan, [ (Di-tert. -butylphosphino) (Di-cyclohexylphosphino] methan oder Bis (di-cyclohexylphosphino)methan deren gute Eignung für das erfindungsgemäße Verfahren derzeit der Methylenverknüpfung der beiden Phosphoratome und der räumlichen Struktur der Reste R1 bis R4 zugeschrieben wird.Diphosphanes which are bridged with a methylene group are preferably used as the chelating ligand; particularly preferably with C 3 - to Cio-cycloaliphatic or branched C 3 - to C rj-aliphatic radicals R 1 to R 4 substituted methylene-bridged diphosphines, such as for example bis (di-tert-butylphosphino) methane, [(Di tert-butylphosphino) (di-cyclohexylphosphino] methane or bis (di-cyclohexylphosphino) methane, the suitability of which for the process according to the invention is currently attributed to the methylene linkage of the two phosphorus atoms and the spatial structure of the radicals R 1 to R 4 .
Eine ganz besonders bevorzugte Verbindung als Chelatligand ist das Bis (di-tert.-butylphosphino)methan.A very particularly preferred compound as the chelating ligand is bis (di-tert-butylphosphino) methane.
Die Liganden L1, L2 tragen je nach formaler Oxidationsstufe des Zentralmetalls M eine oder zwei formal negative Ladungen, oder aber wenn das Metall formal ungeladen ist, so sind die Liganden Li, L2 ebenfalls formal ungeladen.Depending on the formal oxidation state of the central metal M, the ligands L 1 , L 2 carry one or two formally negative charges, or if the metal is formally uncharged, the ligands L i , L 2 are also formally uncharged.
Die chemische Natur der Liganden ist nicht kritisch. Nach dem derzeitigen Kenntnisstand haben sie die Funktion den Rest des Me¬ tallkomplexes gegen Zersetzung, beispielsweise Abscheiden des Me¬ talls oder- unspezifische Reaktionen, beispielsweise Aggregierung der Komplexfragmente, zu stabilisieren.The chemical nature of the ligands is not critical. According to the current state of knowledge, they have the function of stabilizing the rest of the metal complex against decomposition, for example deposition of the metal or non-specific reactions, for example aggregation of the complex fragments.
Geeignete formal geladene anorganische Liganden L1, L2 sind Halogenide, Sulfate, Phosphate oder Nitrate.Suitable formally charged inorganic ligands L 1 , L 2 are halides, sulfates, phosphates or nitrates.
Vorzugsweise verwendet man Halogenide wie Chloride, Bromide, Iodide und insbesondere Chloride.Halides such as chlorides, bromides, iodides and in particular chlorides are preferably used.
Geeignete formal geladene organische Liganden L1, L2 sind Cι~ bis C 0-aliphatische, C3- bis C30-cycloaliphatische, C - bis C20- Aralkylreste mit C6- bis Cι0-Arylrest und Cχ~ bis C10-Alkylrest, C-6- bis C o~aromatische Reste, wie beispielsweise Methyl, Ethyl Propyl, iso-Propyl, tert.-Butyl, neo-Pentyl, Cyclohexyl, Benzyl, Neophyl, Phenyl und substituierte Phenylreste.
Weiterhin eignen sich als formal geladene organische Liganden L1, L2 Cι~ bis C o~Carboxylate wie beispielsweise Acetat, Propionat, Oxalat, Benzoat, Citrat sowie Salze von organischen Sulfonsäuren wie Methylsulfonat, Trifluormethylsulfonat, p-Toluolsulfonat. Vorzugsweise verwendet man Cι~ bis C -Carboxylate, Sulfonsäurede- rivate und insbesondere Acetat und p-Toluolsulfonat.Suitable formally charged organic ligands L 1 , L 2 are C 1 to C 0 aliphatic, C 3 to C 30 cycloaliphatic, C to C 20 aralkyl radicals with C 6 to C 0 aryl radical and C 1 to C 10 -Alkylrest, C- 6 - to C o ~ aromatic residues, such as methyl, ethyl propyl, isopropyl, tert-butyl, neo-pentyl, cyclohexyl, benzyl, neophyl, phenyl and substituted phenyl residues. Also suitable as formally charged organic ligands L 1 , L 2 -C ~ ~ C o ~ carboxylates such as acetate, propionate, oxalate, benzoate, citrate and salts of organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate. Preference is given to -C ~ C carboxylates, sulfonic acid derivatives and in particular acetate and p-toluenesulfonate.
Als formal ungeladene Liganden L1, L2 sind generell Lewisbasen ge¬ eignet, also Verbindungen mit einem freien Elektronenpaar. Beson- ders gut geeignet sind Lewisbasen deren freies Elektronenpaar oder deren freie Elektronenpaare sich an einem Stickstoff- oder Sauerstoffatom befinden, also beispielsweise Nitrile, R-CN, Ke¬ tone, Ether, Alkohole. Vorzugsweise verwendet man Cι~ bis Cirj-Ni- trile wie Acetonitril, Propionitril, Benzonitril oder C2- bis Cirj- Ketone wie Aceton, Acetylaceton oder aber C - bis Cirj-Ether, wie Dirnethylether, Diethylether, Tetrahydrofuran. Insbesondere verwendet man Acetonitril oder Tetrahydrofuran.Lewis bases, that is to say compounds with a free pair of electrons, are generally suitable as formally uncharged ligands L 1 , L 2 . Lewis bases whose free electron pair or whose free electron pairs are located on a nitrogen or oxygen atom, ie, for example, nitriles, R-CN, ketones, ethers, alcohols, are particularly suitable. Preference is given to using C ~ to Cirj-nitriles such as acetonitrile, propionitrile, benzonitrile or C 2 - to Cirj-ketones such as acetone, acetylacetone or else C - to Cirj-ethers such as methyl ether, diethyl ether, tetrahydrofuran. In particular, acetonitrile or tetrahydrofuran is used.
Je nach formaler Ladung des, das Metall M enthaltenden Komplex- fragments, enthält der Metallkomplex (I) Anionen. Ist das M-ent- haltende Komplexfragment formal ungeladen, so enthält der erfindungsgemäße Komplex kein Anion X.Depending on the formal charge of the complex fragment containing the metal M, the metal complex (I) contains anions. If the M-containing complex fragment is formally uncharged, the complex according to the invention contains no anion X.
Die chemische Natur der Anionen X ist nicht kritisch. Nach dem derzeitigen Kenntnisstand ist es jedoch von Vorteil wenn sie mög¬ lichst wenig nucleophil sind, d.h. eine möglichst geringe Tendenz haben mit dem Zentralmetall M eine chemische Bindung einzugehen. Geignete Anionen X sind beispielsweise Perchlorat, Sulfat, Phosphat, Nitrat und Carboxylate, wie beispielsweise Acetat, Tri- fluoracetat, Tri-chloracetat, Propionat, Oxalat, Citrat, Benzoat, sowie konjugierte Anionen von Organosulfonsäuren wie zum Beispiel Methylsulfonat, Trifluormethylsulfonat und para-Toluolsulfonat, weiterhin Tetrafluoroborat, Tetraphenylborat, Tetrakis (pentafluo- rophenyDborat, Hexafluorophosphat, Hexafluoroarsenat oder Hexa- fluoroantimonat. Vorzugsweise verwendet man Perchlorat, Trifluor- acetat, Sulfonate wie Methylsulfonat, Trifluormethylsulfonat, p-Toluolsulfonat, Tetrafluoroborat oder Hexafluorophosphat und insbesondere Trifluoracetat, Perchlorat oder p-Toluolsulfonat.The chemical nature of the anions X is not critical. According to the current state of knowledge, however, it is advantageous if they are as little nucleophilic as possible, i.e. have as little tendency as possible to form a chemical bond with the central metal M. Suitable anions X are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as, for example, methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate , furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyDborat, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate. Preference is given to using perchlorate, trifluoroacetate, sulfonates such as methylsulfonate, trifluoromethyl or toluene fluoronafluorophenate, pentafluorofluorate, pentafluorophenate, pentafluorophorate, Toluenesulfonate.
Als olefinisch ungesättigte Verbindungen kommen grundsätzlich alle Monomere dieser Verbindungsklasse in Betracht.In principle, all monomers of this class of compounds can be considered as olefinically unsaturated compounds.
Geeignet sind besonders Ethylen und C3-Cι0-Alk-l-ene wie Propylen, 1-Buten, 1-Penten, 1-Hexen, 1-Hepten, 1-Octen, 1-Nonen und 1-Decen. Es können auch interne E- oder Z-Olefine wie 2-Buten, 2-Penten, 2- und 3-Hexen, vorteilhaft eingesetzt werden; ferner eignen sich als Monomere Diene wie 1,3-Butadien, 1, 4-Hexadien,
1, 5-Hexadien, sowie daneben Cycloolefine wie Cyclopenten, Cyclo- hexen, Norbornen und Norbornadien, Cyclopentadien und Dicyclo- pentadien.Particularly suitable are ethylene and C 3 -C 1 -alk-1-enes such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen and 1-decene. Internal E or Z olefins such as 2-butene, 2-pentene, 2- and 3-hexene can also be used advantageously; dienes such as 1,3-butadiene, 1,4-hexadiene, 1, 5-hexadiene, and also cycloolefins such as cyclopentene, cyclohexene, norbornene and norbornadiene, cyclopentadiene and dicyclopentadiene.
Als olefinisch ungesättigte aromatische Monomere seien in erster Linie Styrol und α-Methyl-styrol genannt.As olefinically unsaturated aromatic monomers, styrene and .alpha.-methylstyrene may be mentioned primarily.
Besondere Bedeutung als Monomere haben ferner mit funktioneilen Gruppen substituierte Olefine. Als funktionelle Gruppen kommen in Frage die Carboxylgruppe, -COOH und deren Derivate, wie zum Bei- spiel Ester, Halogenide und Amide, ferner die Hydroxylgruppe, die Cyangruppe, -CN, Ketogruppe, Aldehydgruppe und Carboxylatgruppe sowie die Silylgruppe, -SiR3, wobei R Wasserstoff oder ein organi¬ scher Rest mit 1 bis 15 Kohlenstoffatomen bedeutet.Olefins substituted with functional groups are also particularly important as monomers. Possible functional groups are the carboxyl group, -COOH and their derivatives, such as esters, halides and amides, furthermore the hydroxyl group, the cyano group, -CN, keto group, aldehyde group and carboxylate group as well as the silyl group, -SiR 3 , where R is hydrogen or an organic radical having 1 to 15 carbon atoms.
Besonders geeignete, mit funktionellen Gruppen substituierte Olefine sind Acrylsäure und Methacrylsäure sowie deren Derivate, darunter insbesondere die Nitrile, die Amide und die Cι-Cιo-Alkyl- ester wie beispielsweise Acrylnitril, Methacrylnitril, Methyl- acrylat, Ethylacrylat, Propylacrylat, Butylacrylat, tert.-Butyl- acrylat, 2-Ethylhexylacrylat, Methylmethacrylat, Ethylmeth- acrylat, Propylmethacrylat. Weitere geeignete Monomere sind Vinylchlorid, Vinylacetat, Vinylpropionat, Maleinsäureanhydrid und N-Vinylpyrrolidon.Particularly suitable olefins substituted with functional groups are acrylic acid and methacrylic acid and their derivatives, including in particular the nitriles, the amides and the C 1 -C 8 -alkyl esters such as, for example, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tert. -Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate. Other suitable monomers are vinyl chloride, vinyl acetate, vinyl propionate, maleic anhydride and N-vinyl pyrrolidone.
Selbstverständlich können auch Mischungen verschiedener Monomeren eingesetzt werden.Mixtures of different monomers can of course also be used.
Das molare Verhältnis zwischen den unterschiedlichen Monomeren kann weitgehend frei gewählt werden.The molar ratio between the different monomers can largely be chosen freely.
Die Polymerisationsbedingungen sind an sich unkritisch. Die Poly¬ merisationen können sowohl absatzweise als auch kontinuierlich durchgeführt werden.The polymerization conditions are not critical per se. The polymerizations can be carried out batchwise or continuously.
Drücke von 100 bis 500000 kPa, vorzugsweise 200 bis 350000 kPa und insbesondere 500 bis 30000 kPa, Temperaturen von (-50) bis 400°C, bevorzugt 20 bis 250°C und insbesondere 40 bis 150°C haben sich als geeignet erwiesen.Pressures of 100 to 500,000 kPa, preferably 200 to 350,000 kPa and in particular 500 to 30,000 kPa, temperatures of (-50) to 400 ° C, preferably 20 to 250 ° C and in particular 40 to 150 ° C have proven to be suitable.
Polymerisationsreaktionen mit Hilfe der erfindungsgemäßenPolymerization reactions using the inventive
Katalysatorsysteme lassen sich in der Gasphase, in Suspension, in flüssigen und in überkritischen Monomeren und in, unter den Poly¬ merisationsbedingungen inerten, Lösungsmitteln durchführen.Catalyst systems can be carried out in the gas phase, in suspension, in liquid and in supercritical monomers and in solvents which are inert under the polymerization conditions.
Geeignete inerte Lösungsmittel sind Alkohole wie Methanol, Ethanol, Propanol, i-Propanol, 1-Butanol und tert.-Butanol, Sulfoxide und Sulfone, beispielsweise Dimethylsulfoxid, Ester wie
Essigester und Butyrolacton, Ether wie Tetrahydrofuran, Dimethyl- ethylenglycol und Diisopropylether sowie aromatische Lösungs¬ mittel wie Benzol, Toluol, Ethylbenzol oder Chlorbenzol oder Gemische derselben.Suitable inert solvents are alcohols such as methanol, ethanol, propanol, i-propanol, 1-butanol and tert-butanol, sulfoxides and sulfones, for example dimethyl sulfoxide, esters such as Ethyl acetate and butyrolactone, ethers such as tetrahydrofuran, dimethylethylene glycol and diisopropyl ether and aromatic solvents such as benzene, toluene, ethylbenzene or chlorobenzene or mixtures thereof.
Das Molekulargewicht der erfindungsgemäßen Polymere läßt sich durch die Variation der Polymerisationstemperatur und durch den Zusatz von Wasserstoff in üblicher Weise regeln.The molecular weight of the polymers according to the invention can be regulated in a customary manner by varying the polymerization temperature and by adding hydrogen.
Die unter Verwendung des erfindungsgemäßen Verfahrens herge¬ stellten Polymere zeichnen sich im allgemeinen durch eine hohe Molmasse, enge Molmassenverteilung und hohen Anteil an Doppel¬ bindungen aus.The polymers produced using the process according to the invention are generally distinguished by a high molar mass, narrow molar mass distribution and high proportion of double bonds.
Die Polymere eignen sich zur Herstellung von Formkörpern, ins¬ besondere von Formkörpern für Verpackungen und sowie von Folien und Fasern und für Haftvermittler und lassen sich aufgrund ihrer reaktiven Doppelbindungen leicht chemisch modifizieren.The polymers are suitable for the production of moldings, in particular moldings for packaging and for films and fibers and for adhesion promoters, and can be easily chemically modified on account of their reactive double bonds.
Beispiele 1 bis 4Examples 1 to 4
In einem 0, 3-1-Autoklaven wurden 75 ml des Lösungsmittels (Bei¬ spiel 1 und 4 Methanol, Beispiel 2 und 3 Toluol) und der entspre¬ chende Palladiumkomplex (siehe Tabelle 1) vorgelegt. Danach wurde bei der gewünschten Temperatur Ethylen bis zu dem Gesamtdruck von 6000 kPa (siehe Tabelle 1) aufgepreßt und 5 Stunden lang polymer- isiert. Die Reaktionstemperatur und der Druck wurden während der gesamten Reaktionsdauer konstant gehalten, wonach die Polymeri¬ sation durch Abkühlen und Entspannen des Autoklaven abgebrochen, das Reaktionsgemisch filtriert und das Polymerisat isoliert wurde.75 ml of the solvent (examples 1 and 4 methanol, examples 2 and 3 toluene) and the corresponding palladium complex (see Table 1) were placed in a 0.3-1 autoclave. Then ethylene was injected at the desired temperature up to the total pressure of 6000 kPa (see Table 1) and polymerized for 5 hours. The reaction temperature and the pressure were kept constant throughout the reaction, after which the polymerization was stopped by cooling and releasing the pressure in the autoclave, the reaction mixture was filtered and the polymer was isolated.
Die Verfahrensparameter, eingesetzte Mengen an Katalysator und Lösungsmittel sowie die erhaltenen Mengen an Polymerisat und deren Schmelzpunkte (bestimmt mit der Methode der DSC) sind der Tabelle 1 zu entnehmen.The process parameters, amounts of catalyst and solvent used and the amounts of polymer obtained and their melting points (determined by the DSC method) can be found in Table 1.
Erläuterung der Abkürzungen:Explanation of the abbreviations:
dtbpm = Bis (di-tert.-butylphosphino)methan MeCN = Acetonitril
Tabelle: Verfahrensparameter, Polymereigenschaftendtbpm = bis (di-tert-butylphosphino) methane MeCN = acetonitrile Table: Process parameters, polymer properties
Bsp. Katalysator/ Tempe - Ausbeute Schmelz¬ (mmol) ratur [gl punktExample catalyst / temperature - yield of melting (mmol) temperature [Eq
[°C] [°C][° C] [° C]
1 [(dtbpm)Pd(MeCN)2] (CF3C02)2 85 2 1051 [(dtbpm) Pd (MeCN) 2 ] (CF 3 C0 2 ) 2 85 2 105
2 [ (dtbpm)Pd(MeCN)2] (C104)2 70 1-5 1462 [(dtbpm) Pd (MeCN) 2 ] (C10 4 ) 2 70 1-5 146
3 [(Ph2P CH2-3PPh2)Pd(MeCN)2] (C104)2 70 0,5 1433 [(Ph 2 P CH 2 - 3 PPh 2 ) Pd (MeCN) 2 ] (C10 4 ) 2 70 0.5 143
4 [ (dtbpm)Pd(MeCN)2] (CF3S03)2 50 0,8 122
4 [(dtbpm) Pd (MeCN) 2 ] (CF 3 S0 3 ) 2 50 0.8 122
Claims
PatentansprücheClaims
1. Polymere, erhältlich durch Polymerisation von olefinisch ungesättigten Monomeren in Gegenwart eines Metallkomplexes der allgemeinen Formel (I)1. Polymers obtainable by polymerizing olefinically unsaturated monomers in the presence of a metal complex of the general formula (I)
M ein Metall aus der Gruppe VIIIB des Perioden¬ systems der ElementeM is a metal from group VIIIB of the Periodic Table of the Elements
Ei, E2 ein Element aus der Gruppe VA des Periodensystems der Elemente,E i , E 2 an element from group VA of the periodic table of the elements,
eine verbrückende Struktureinheit aus einer, zwei oder drei Substruktureinheiten von Elementen der Gruppe IVA, VA, VIA des Periodensystems der Elemente,a bridging structural unit consisting of one, two or three substructural units from elements of group IVA, VA, VIA of the periodic table of the elements,
R1 bis R4 Substituenten, ausgewählt aus der Gruppe bestehend aus Cι~ bis C2n-Kohlenstofforganischen und C3- bis C3o-Siliciumorganischen Reste, wobei die Reste ein Element oder mehrere Elemente der Gruppe IVA, VA, VIA und VIIA des Periodensystems der Elemente ent- halten können,R 1 to R 4 substituents selected from the group consisting of -C ~ to C 2 n-organic carbon and C 3 - to C 3 o-organosilicon radicals, the radicals being one or more elements from the group IVA, VA, VIA and VIIA of the periodic table of the elements,
Li, L2 formal geladene oder neutrale LigandenL i , L 2 formally charged or neutral ligands
ein- oder mehrwertige Anionenmono- or polyvalent anions
0, 1 oder 20, 1 or 2
m, n 0, 1 oder 2m, n 0, 1 or 2
wobei p = m x n
2. Polymere nach Anspruch 1 wobei Z eine verbrückende Struktur- einheit mit einem, zwei oder drei Brückenatomen aus der Gruppe IVA des Periodensystems der Elemente bedeutet.where p = mxn 2. Polymers according to claim 1, wherein Z is a bridging structural unit with one, two or three bridge atoms from group IVA of the periodic table of the elements.
3. Polymere nach den Ansprüchen 1 bis 2, wobei Z -CR5R6- oder -SiR5R6- bedeutet und R5 und R6 für Wasserstoff, Ci- bis Cio-Kohlenstofforganischer Rest steht.3. Polymers according to claims 1 to 2, wherein Z is -CR 5 R 6 - or -SiR 5 R 6 - and R 5 and R 6 are hydrogen, Ci to Cio-carbon organic radical.
Polymere nach den Ansprüchen 1 bis 3, wobei Ex und E2 Phosphor bedeutet.Polymers according to claims 1 to 3, wherein E x and E 2 is phosphorus.
Polymere nach den Ansprüchen 1 bis 4, wobei R1 bis R4 Cι~ bis C o-aliphatischer oder C3- bis C20-cycloaliphatischer Rest be¬ deutet.Polymers according to claims 1 to 4, wherein R 1 to R 4 is C 1 -C 8 -aliphatic or C 3 - to C 20 -cycloaliphatic radical.
Verfahren zur Herstellung von Polymeren aus olefinisch ungesättigten Monomeren durch Polymerisation von ungesättigten Monomeren in Gegenwart eines Metallkomplexes der allgemeinen Formel (I)Process for the preparation of polymers from olefinically unsaturated monomers by polymerizing unsaturated monomers in the presence of a metal complex of the general formula (I)
M ein Metall aus der Gruppe VIIIB des Perioden¬ systems der ElementeM is a metal from group VIIIB of the Periodic Table of the Elements
Ei, E2 ein Element aus der Gruppe VA des Periodensystems der Elemente,Ei, E 2 an element from group VA of the Periodic Table of the Elements,
eine verbrückende Struktureinheit aus einer, zwei oder drei Substruktureinheiten von Elementen der Gruppe IVA, VA, VIA des Periodensystems der Elemente,a bridging structural unit consisting of one, two or three substructural units from elements of group IVA, VA, VIA of the periodic table of the elements,
Ri bis R4 Substituenten, ausgewählt aus der Gruppe bestehend aus Cχ~ bis C2o-Kohlenstofforganischen und C3- bis C3o-Siliciumorganischen Reste, wobei die Reste ein Element oder mehrere Elemente der Gruppe IVA, VA,
VIA und VIIA des Periodensystems der Elemente ent¬ halten können,R i to R 4 substituents selected from the group consisting of Cχ ~ to C 2 o -organic carbon and C 3 - to C 3 o-organosilicon radicals, the radicals being one or more elements from group IVA, VA, VIA and VIIA of the periodic table of the elements can contain,
L1, L2 formal geladene oder neutrale LigandenL 1 , L 2 formally charged or neutral ligands
X ein- oder mehrwertige AnionenX mono- or polyvalent anions
p 0, 1 oder 2p 0, 1 or 2
m, n 0, 1 oder 2m, n 0, 1 or 2
wobei p = m x nwhere p = m x n
7. Verfahren nach Anspruch 6, in welchem man als olefinisch un- gesättigte Verbindungen Olefine, Diolefine oder mit funktio¬ neilen Gruppen substituierte Olefine sowie Vinylaromaten ein¬ setzt.7. The method according to claim 6, in which one uses as olefinically unsaturated compounds olefins, diolefins or olefins substituted with functional groups and vinylaromatics.
8. Verfahren nach den Ansprüchen 6 bis 7, in welchem als olefinisch ungesättigte Verbindungen C2- bis C2o~Alk-l-ene, interne C - bis C rj-Alkene, C - bis C2rj-Diolefine oder α-ß-ungesättigte Carbonsäuren oder deren Derivate eingesetzt werden.8. The method according to claims 6 to 7, in which as olefinically unsaturated compounds C 2 - to C 2 o ~ alk-l-enes, internal C - to C rj-alkenes, C - to C 2 rj-diolefins or α- β-unsaturated carboxylic acids or their derivatives are used.
9. Verwendung der Polymeren gemäß der Ansprüche 1 bis 5 als Folien, Fasern oder Formkörper.9. Use of the polymers according to claims 1 to 5 as films, fibers or moldings.
10. Folien, Fasern und Formkörper aus den Polymeren gemäß der An¬ sprüche 1 bis 5.
10. Films, fibers and moldings made of the polymers according to claims 1 to 5.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96914188A EP0827515B1 (en) | 1995-05-22 | 1996-05-09 | Process for the preparation of polymers of olefinically unsaturated monomers |
| DE59605823T DE59605823D1 (en) | 1995-05-22 | 1996-05-09 | METHOD FOR PRODUCING POLYMERS FROM OLEFINICALLY UNSATURATED MONOMERS |
| JP8535311A JPH11505288A (en) | 1995-05-22 | 1996-05-09 | Preparation of polymers of olefinically unsaturated monomers |
| US08/952,440 US6031057A (en) | 1995-05-22 | 1996-05-09 | Polymers of olefinically unsaturated monomers |
| AT96914188T ATE195956T1 (en) | 1995-05-22 | 1996-05-09 | METHOD FOR PRODUCING POLYMERS FROM OLEFINICALLY UNSATURATED MONOMERS |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19518736 | 1995-05-22 | ||
| DE19518736.9 | 1995-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996037522A1 true WO1996037522A1 (en) | 1996-11-28 |
Family
ID=7762557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1996/001964 WO1996037522A1 (en) | 1995-05-22 | 1996-05-09 | Polymers of olefinically unsaturated monomers |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6031057A (en) |
| EP (1) | EP0827515B1 (en) |
| JP (1) | JPH11505288A (en) |
| CN (1) | CN1198168A (en) |
| AT (1) | ATE195956T1 (en) |
| DE (1) | DE59605823D1 (en) |
| WO (1) | WO1996037522A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998047934A1 (en) * | 1997-04-22 | 1998-10-29 | E.I. Du Pont De Nemours And Company | Polymerization of olefins |
| WO1999047569A1 (en) * | 1998-03-19 | 1999-09-23 | Basf Aktiengesellschaft | Method for producing copolymers from functionalised olefinically unsaturated monomers and non-polar olefinically unsaturated compounds |
| US6103658A (en) * | 1997-03-10 | 2000-08-15 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
| US6117959A (en) * | 1998-09-02 | 2000-09-12 | Eastman Chemical Company | Polyolefin catalysts |
| US6174976B1 (en) | 1998-02-24 | 2001-01-16 | Eastman Chemical Company | Neutral nickel complexes for olefin polymerization |
| US6245871B1 (en) | 1997-04-18 | 2001-06-12 | Eastman Chemical Company | Group 8-10 transition metal olefin polymerization catalysts |
| US6265506B1 (en) * | 1997-06-09 | 2001-07-24 | The B. F. Goodrich Company | Method for the preparation of copolymers of ethylene/norbornene-type monomers with cationic palladium catalysts |
| WO2002002573A1 (en) * | 2000-07-06 | 2002-01-10 | Basf Aktiengesellschaft | Metallic compounds and the use thereof in the polymerisation of olefins |
| US6372682B2 (en) | 1997-03-13 | 2002-04-16 | Eastman Chemical Company | Catalyst compositions for the polymerization of olefins |
| US6521724B2 (en) | 2000-03-10 | 2003-02-18 | E. I. Du Pont De Nemours And Company | Polymerization process |
| US6620896B1 (en) | 1999-02-23 | 2003-09-16 | Eastman Chemical Company | Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom |
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| US6255419B1 (en) * | 1997-02-07 | 2001-07-03 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst and process for producing olefin polymers |
| US6660677B1 (en) * | 1997-03-10 | 2003-12-09 | Eastman Chemical Company | Supported group 8-10 transition metal olefin polymerization catalysts |
| US6252022B1 (en) * | 1998-05-29 | 2001-06-26 | E. I. Du Pont De Nemours And Company | Molecular weight control in olefin polymerization |
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| EP0454231A2 (en) * | 1990-04-20 | 1991-10-30 | The University Of North Carolina At Chapel Hill | Late transition metal catalysts for olefin polymerization |
| EP0610601A1 (en) * | 1993-02-06 | 1994-08-17 | ENICHEM S.p.A. | Process for preparing polymers based on carbon monoxide and olefins |
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| US3051694A (en) * | 1958-11-17 | 1962-08-28 | American Cyanamid Co | Polymerizing substituted acetylenes using nickel-carbonyl complex catalysts |
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| EP0589527B1 (en) * | 1992-09-21 | 1999-07-28 | Montell Technology Company bv | Polymerization process |
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- 1996-05-09 AT AT96914188T patent/ATE195956T1/en not_active IP Right Cessation
- 1996-05-09 DE DE59605823T patent/DE59605823D1/en not_active Expired - Lifetime
- 1996-05-09 CN CN96194091A patent/CN1198168A/en active Pending
- 1996-05-09 EP EP96914188A patent/EP0827515B1/en not_active Expired - Lifetime
- 1996-05-09 US US08/952,440 patent/US6031057A/en not_active Expired - Fee Related
- 1996-05-09 WO PCT/EP1996/001964 patent/WO1996037522A1/en active IP Right Grant
- 1996-05-09 JP JP8535311A patent/JPH11505288A/en not_active Ceased
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| EP0454231A2 (en) * | 1990-04-20 | 1991-10-30 | The University Of North Carolina At Chapel Hill | Late transition metal catalysts for olefin polymerization |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6103658A (en) * | 1997-03-10 | 2000-08-15 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
| US6303720B1 (en) | 1997-03-10 | 2001-10-16 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
| US6844404B2 (en) | 1997-03-13 | 2005-01-18 | Eastman Chemical Company | Catalyst compositions for the polymerization of olefins |
| US6372682B2 (en) | 1997-03-13 | 2002-04-16 | Eastman Chemical Company | Catalyst compositions for the polymerization of olefins |
| US6245871B1 (en) | 1997-04-18 | 2001-06-12 | Eastman Chemical Company | Group 8-10 transition metal olefin polymerization catalysts |
| US6656869B2 (en) | 1997-04-18 | 2003-12-02 | Eastman Chemical Company | Group 8-10 transition metal olefin polymerization catalysts |
| WO1998047934A1 (en) * | 1997-04-22 | 1998-10-29 | E.I. Du Pont De Nemours And Company | Polymerization of olefins |
| US6265506B1 (en) * | 1997-06-09 | 2001-07-24 | The B. F. Goodrich Company | Method for the preparation of copolymers of ethylene/norbornene-type monomers with cationic palladium catalysts |
| US6174976B1 (en) | 1998-02-24 | 2001-01-16 | Eastman Chemical Company | Neutral nickel complexes for olefin polymerization |
| WO1999047569A1 (en) * | 1998-03-19 | 1999-09-23 | Basf Aktiengesellschaft | Method for producing copolymers from functionalised olefinically unsaturated monomers and non-polar olefinically unsaturated compounds |
| US6117959A (en) * | 1998-09-02 | 2000-09-12 | Eastman Chemical Company | Polyolefin catalysts |
| US6365539B1 (en) | 1998-09-02 | 2002-04-02 | Eastman Chemical Company | Polyolefin catalysts |
| US6620896B1 (en) | 1999-02-23 | 2003-09-16 | Eastman Chemical Company | Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom |
| US6521724B2 (en) | 2000-03-10 | 2003-02-18 | E. I. Du Pont De Nemours And Company | Polymerization process |
| US6812306B2 (en) | 2000-07-06 | 2004-11-02 | Basf Aktiengesellschaft | Metallic compounds and the use thereof in the polymerization of olefins |
| WO2002002573A1 (en) * | 2000-07-06 | 2002-01-10 | Basf Aktiengesellschaft | Metallic compounds and the use thereof in the polymerisation of olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| US6031057A (en) | 2000-02-29 |
| DE59605823D1 (en) | 2000-10-05 |
| JPH11505288A (en) | 1999-05-18 |
| EP0827515B1 (en) | 2000-08-30 |
| EP0827515A1 (en) | 1998-03-11 |
| ATE195956T1 (en) | 2000-09-15 |
| CN1198168A (en) | 1998-11-04 |
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